JPH117129A - Positive photoresist composition and multilayered resist material using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist compsn. showing a good film remaining rate for the formation of a pattern, especially not a dense pattern of lines and spaces(L& S) but an isolated pattern, excellent development contrast between an exposed part and a part not exposed, and excellent resolution, latitude for exposure, focus depth characteristics and cross section. SOLUTION: This compsn. contains (A) an alkali-soluble resin, (B) a compd. containing quinone diazide groups, such as 2,4-bis[4-hydroxy-3-(4- hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol naphthoquinone diazide sulfonic acid ester and (C) halogenated sulfonic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition and a multilayer resist material using the same, and more particularly to a method for forming an isolated pattern, not a dense pattern of lines and spaces (L & S). Positive photoresist composition capable of forming a resist pattern having a good residual film ratio, excellent development contrast between exposed and unexposed areas, excellent resolution, exposure latitude, depth of focus characteristics and cross-sectional shape, and the positive photoresist The present invention relates to a multilayer resist material using a composition.

[0002]

2. Description of the Related Art Hitherto, a photoresist composition comprising an alkali-soluble resin and a quinonediazide group-containing compound has been sufficiently used in the production of semiconductor devices and liquid crystal devices because of its excellent resolution, sensitivity and etching resistance. ing. In recent VLSI fabrication, high resolution of 0.4 μm or 0.35 μm or less, which is half a micron or less, is required, and further, excellent resolution, exposure latitude, depth of focus width characteristics, and shape. There is a demand for a photoresist composition capable of forming a well-defined rectangular resist pattern. However, in the formation of a fine pattern of 0.4 μm or less, it is difficult to provide a rectangular resist pattern having an excellent cross-sectional shape. It began to appear and it was easy to become a tapered pattern. In particular, the change rate of the pattern shape due to the shift of the focal point position is large (poor depth of focus width characteristic), and the film decrease phenomenon appears on the plus side (the focal point is closer to the substrate side than the resist film surface), and the minus side (the focal point is (Above the surface of the resist film), a phenomenon in which the pattern became thinner overall was observed.
This was more pronounced when an isolated pattern was formed than when a dense pattern was formed. For this reason, the conventional photoresist composition has a very narrow range of the margin of defocus that can obtain a good pattern shape, and as a result, in an actual exposure operation,
There has been a problem that a slight deviation of the focus causes variation in the pattern shape.

As a means for preventing a phenomenon in which a pattern shape is deformed by reflection of light from a highly reflective underlying substrate such as a silicon substrate, an aluminum film, a tungsten silicide film or the like, an antireflection film is provided between the substrate and the photoresist film. (BARC method) has been proposed, however, the photoresist film formed on the antireflection film has a drawback that the bottom of the resist pattern is easily pulled down. Further, when the focal position is shifted on the plus side, the film thickness tends to be further reduced, and when the focal position is shifted on the minus side, the film tends to be thinner.

[0004] In view of the above, as a means for improving the depth of focus characteristic especially on the plus side, when a sulfonic acid halide having a specific structure is added to a photoresist composition, the bottom of the bottom portion and the pattern top portion are reduced. The present inventors have found that the film has an effect of suppressing the film thickness reduction, and reported it in Japanese Patent Application No. 8-305873. This makes it possible to improve the focal depth width characteristic on the plus side on the anti-reflection film as well as on the substrate on which the anti-reflection film is not formed. , That is, a photoresist film excellent in the focal depth width characteristic was obtained.

However, on the contrary, when the focus shifts on the minus side, a phenomenon occurs in which the pattern top becomes large and the bottom becomes narrow, resulting in a pattern having a cross-section just like a feather plate. However, there is a problem that the pattern is likely to collapse. This is especially
The tendency is stronger in the case of forming an isolated pattern than in the case of forming a dense pattern, as the pattern becomes finer, and as the focus tilts to the minus side,
The tendency increases.

It is considered that the reason why the pattern tends to be reduced on the plus side of the focal point is that the exposure amount is exceeded because the distance between the light source and the substrate is shorter than the specified position. It is considered that the phenomenon that the isolated pattern becomes thinner as a whole easily occurs because light is more likely to be reflected from the underlying substrate than in a dense pattern shape. Therefore, it has been desired to realize a positive photoresist composition that can form a pattern having a good shape regardless of whether the focal point is shifted to the plus side or the minus side.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is not to form a dense pattern of lines and spaces (L & S) but to form an isolated pattern. An object of the present invention is to provide a positive photoresist composition capable of forming a resist pattern excellent in development contrast, resolution, exposure latitude, depth of focus characteristics, and cross-sectional shape, and a multilayer resist material using the positive photoresist composition.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention provides (A) an alkali-soluble resin, (B) the following general formula (I)

[0009]

Embedded image

(Wherein R ^{1 to} R ⁹ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or alkoxy group having 1 to 5 carbon atoms). At least one kind of a quinonediazide group-containing compound in which part or all of the hydroxyl groups of the compound to be obtained is esterified with quinonediazidesulfonic acid, and (C) the following general formula (II)

[0011]

Embedded image R ¹⁰ —SO ₂ —X (II)

(Wherein, R ¹⁰ represents an alkyl group, an alkyl group having a substituent, an alkenyl group, an aryl group or an aryl group having a substituent, and X represents F or Cl)
A positive photoresist composition comprising at least one sulfonic acid halide represented by the formula:

The present invention further provides (D) a compound represented by the following general formula (III):

[0014]

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(Wherein R ¹¹ and R ¹² may be the same or different, and each represents a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,
Alkenyl group and alkoxy group) are provided.

Furthermore, the present invention further provides (E) a sensitivity improver represented by the following general formula (IV):

[0017]

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(Wherein, R ^{13 to} R ²⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms,
R ^{21 to} R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q represents a hydrogen atom or 1 carbon atom; To 6 alkyl groups, a cyclo ring having 3 to 6 carbon atom chains bonded to R ²¹ , or a residue represented by the following chemical formula:

[0019]

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Wherein R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, or a cycloalkyl group; Represents an integer of 1 to 3);
a and b each represent an integer of 1 to 3; d represents an integer of 0 to 3; n represents 0 to 2]. It is.

Further, the present invention provides the above positive photoresist composition, wherein the content of the component (C) is 0.01 to 5% by weight based on the total solid content of the composition. Is what you do.

Further, the present invention provides the above positive photoresist composition, wherein the content of the component (D) is 0.01 to 10% by weight based on the total solid content of the composition. Things.

Further, in the present invention, the compounding ratio of the (B) quinonediazide group-containing compound is 10 to 60 with respect to the total amount of (A) the alkali-soluble resin and (E) the sensitivity improver added as required. It is intended to provide the above positive photoresist composition in a percentage by weight.

Further, the present invention provides a multilayer resist material comprising an antireflection layer on a substrate and a positive photoresist layer on the antireflection layer, wherein the positive photoresist layer is formed from the positive photoresist composition. It is intended to provide a formed multilayer resist material.

Japanese Patent Application Laid-Open No. 8-129255 describes a photosensitive component similar to the component (B) used in the present invention, but a photoresist composition using the photosensitive component disclosed in the publication is disclosed. Cannot improve the focal depth width characteristics on the plus side and the minus side at the same time. In particular, the photoresist composition described in the publication cannot provide sufficient depth of focus characteristics when an antireflection film is used.

(A) Alkali-Soluble Resin The alkali-soluble resin as the component (A) is not particularly limited, and may be arbitrarily selected from those which can be generally used as a film-forming substance in a positive photoresist composition. Preferably, a condensation reaction product of an aromatic hydroxy compound with an aldehyde or a ketone, polyhydroxystyrene and a derivative thereof can be given.

The aromatic hydroxy compound includes, for example, phenol, m-cresol, p-cresol, o
-Xylenols such as cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3, 5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-
Butylphenol, 2-tert-butylphenol,
2-tert-butyl-4-methylphenol, 2-t
alkylphenols such as tert-butyl-5-methylphenol; alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol; Isopropenylphenol, p-isopropenylphenol, 2-
Methyl-4-isopropenylphenol, 2-ethyl-
Isopropenylphenols such as 4-isopropenylphenol; arylphenols such as phenylphenol; polyhydroxyphenols such as 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, and pyrogallol. These may be used alone or in combination of two or more.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furyl acrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α -Phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde , P-chlorobenzaldehyde And cinnamic aldehyde. These may be used alone or in combination of two or more.

Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone and the like. These may be used alone or in combination of two or more. Furthermore, aldehydes and ketones may be used in an appropriate combination.

The condensation reaction product of the aromatic hydroxy compound with the aldehyde or ketone can be produced by a known method in the presence of an acidic catalyst. Hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid and the like can be used as the acidic catalyst at that time.

Examples of the polyhydroxystyrene and derivatives thereof include homopolymers of vinylphenol and copolymers of vinylphenol with comonomers copolymerizable therewith. Examples of the comonomer include acrylic acid derivatives, acrylonitrile, methacrylic acid derivatives, methacrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, and p-methylstyrene.
Styrene derivatives such as methoxystyrene and p-chlorostyrene are exemplified.

Among them, alkali-soluble resins suitable as the component (A) in the present invention include m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol and the like. A novolak resin obtained by cutting a low molecular weight region obtained by reacting a phenol with an aldehyde such as formaldehyde is preferable because of its excellent heat resistance. The weight average molecular weight of this novolak resin is 2000 to 250
00, preferably 2,500 to 20,000, more preferably 3,000 to 5,000. Here, the weight average molecular weight is a value in terms of polystyrene determined by gel permeation chromatography (GPC). The cutting of the low molecular weight region can be performed by a process such as separation. In this treatment, the resin obtained by the condensation reaction is dissolved in a good solvent, for example, an alcohol such as methanol or ethanol, a ketone such as acetone or methyl ethyl ketone, or ethylene glycol monoethyl ether acetate or tetrahydrofuran, and then poured into water to precipitate. And so on.

(B) Quinonediazide Group-Containing Compound The quinonediazide group-containing compound as the component (B) is a photosensitive component, and is an esterified product of a quinonediazidesulfonic acid and a compound represented by the general formula (I). Examples of the quinonediazidesulfonic acids include naphthoquinone-1,2-diazidosulfonic acid, orthobenzoquinonediazidosulfonic acid, orthoanthraquinonediazidesulfonic acid, and the like, which are arbitrarily selected from those commonly used without particular limitation. Preferred are naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-
Diazide-4-sulfonyl chloride, naphthoquinone-
And naphthoquinone-1,2-diazidosulfonyl halides such as 1,2-diazide-6-sulfonyl chloride.

The compound represented by the general formula (I) includes
For example, 2,4-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [2-hydroxy-3
(4-hydroxybenzyl) -5-ethylbenzyl]-
6-cyclohexylphenol, 2,4-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-propylbenzyl] -6-cyclohexylphenol, 2,4
-Bis [2-hydroxy-3 (4-hydroxybenzyl) -5-methoxybenzyl] -6-cyclohexylphenol, 2,4-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-ethoxybenzyl]- 6-cyclohexylphenol, 2,4-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-ethenylbenzyl] -6-cyclohexylphenol, 2,4-bis [2-hydroxy-3 (3-hydroxy Benzyl) -5
-Methylbenzyl] -6-cyclohexylphenol,
2,4-bis [2-hydroxy-3 (5-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3 (4-
(Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3 (4-hydroxybenzyl) -5-ethylbenzyl] -6-cyclohexylphenol, 2,4-bis [ 4-hydroxy-3 (4-hydroxybenzyl) -5
-Propylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3 (4-hydroxybenzyl) -5-methoxybenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3
(4-hydroxybenzyl) -5-ethoxybenzyl]
-6-cyclohexylphenol, 2,4-bis [4-
Hydroxy-3 (4-hydroxybenzyl) -5-ethenylbenzyl] -6-cyclohexylphenol, 2,
4-bis [4-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -3-methyl-6-cyclohexylphenol, 2,4-bis [4-hydroxy-
3 (4-hydroxybenzyl) -5-ethylbenzyl]
-3-methyl-6-cyclohexylphenol, 2,4
-Bis [4-hydroxy-3 (4-hydroxybenzyl) -5-methoxybenzyl] -3-methyl-6-cyclohexylphenol, 2,4-bis [4-hydroxy-3 (4-hydroxybenzyl) -5- Ethenylbenzyl] -3-methyl-6-cyclohexylphenol,
2,4-bis [4-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -3-ethyl-6-cyclohexylphenol, 2,6-bis [4-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -4-cyclohexylphenol, 2,6-bis [4-hydroxy-3 (4-hydroxybenzyl) -5
-Ethylbenzyl] -4-cyclohexylphenol,
2,6-bis [4-hydroxy-3 (4-hydroxybenzyl) -5-methoxybenzyl] -4-cyclohexylphenol, 2,6-bis [4-hydroxy-3 (4
-Hydroxybenzyl) -5-ethenylbenzyl] -4
-Cyclohexylphenol, 2,6-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -4-cyclohexylphenol, 2,6-bis [2-hydroxy-3 (4-hydroxybenzyl) −
5-ethylbenzyl] -4-cyclohexylphenol, 2,6-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-methoxybenzyl] -4-cyclohexylphenol, 2,6-bis [2-hydroxy- 3
(4-hydroxybenzyl) -5-ethenylbenzyl]
-4-cyclohexylphenol and the like, particularly 2,4-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy- 3 (4-
Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol is preferred.

In addition to the quinonediazidesulfonic acid ester of the compound represented by formula (I), an esterified product of another hydroxy compound and a quinonediazidesulfonic acid may be used in combination as the photosensitive component. Other hydroxy compounds include, for example, the following (i)
To (iii). (I) Polyhydroxybenzophenones: Examples of compounds belonging to this group include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone,
2,3,4,4′-tetrahydroxybenzophenone,
2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4,4 ′, 6-pentahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′ , 3,4,5′-pentahydroxybenzophenone, 2,3 ′, 4,5,5′-pentahydroxybenzophenone, 2,3,3 ′, 4
4 ', 5'-hexahydroxybenzophenone and the like.

(Ii) The following general formula (IV)

[0037]

Embedded image

(Wherein, R ^{13 to} R ²⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms,
R ^{21 to} R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q represents a hydrogen atom or 1 carbon atom; To 6 alkyl groups, a cyclo ring having 3 to 6 carbon atom chains bonded to R ²¹ , or a residue represented by the following chemical formula:

[0039]

Embedded image

Wherein R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, or a cycloalkyl group; Represents an integer of 1 to 3);
a and b each represent an integer of 1 to 3; d represents an integer of 0 to 3; n represents an integer of 0 to 2]. [2
-Hydroxy-3 (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,
5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenyl Methane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-
Hydroxyphenylmethane, bis (4-hydroxy-
2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl)- 3,
4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, Bis (4-hydroxyphenyl) -3-methoxy-
4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4- Hydroxyphenyl) -4
-Hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4)
-Hydroxy-6-methylphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methyl) Phenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3
-Cyclohexyl-6-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-
6-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4)
-Methylphenyl) -2-hydroxyphenylmethane,
Bis (4-hydroxy-2-methyl-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane,
Bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -3,4-dihydroxyphenylmethane, 1-
[1- (4-hydroxyphenyl) isopropyl] -4
-[1,1-bis (4-hydroxyphenyl) ethyl]
Benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, bis (4-hydroxy-2, 3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,
3,5-trimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,3,5- Hydroxyaryl compounds such as trimethylphenyl) -4-hydroxy-3-methoxyphenylmethane; 2- (2,3,4-
Trihydroxyphenyl) -2- (2 ', 3', 4'-
Trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane Bis (hydroxyphenyl) alkane compounds such as bis (2,3,4-trihydroxyphenyl) methane and bis (2,4-dihydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-
And bis (hydroxyphenyl) cycloalkane compounds such as bis (2-methyl-4-hydroxyphenyl) cyclohexane.

Also, 2,6-bis [1- (2,4-dihydroxyphenyl) isopropyl] -4-methylphenol, 4,6-bis [1- (4-hydroxyphenyl)
Isopropyl] resorcin, 4,6-bis (3,5-dimethoxy-4-hydroxyphenylmethyl) pyrogallol, 4,6-bis (3,5-dimethyl-4,6-dihydroxyphenylmethyl) -4-methylphenol, 2,
6-bis (2,3,4-trihydroxyphenylmethyl) -4-methylphenol and the like.

(Iii) Phenols: Examples of compounds belonging to this group include phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, Phenols such as gallic acid, partially esterified or partially etherified gallic acid, and the like.

The quinonediazide group-containing compound (B) used in the present invention is obtained by subjecting the above-mentioned quinonediazidesulfonic acid and the above-mentioned formula (I) or the above-mentioned hydroxy compound to a condensation reaction to be completely or partially esterified. Can be manufactured by This condensation reaction is usually advantageously carried out in an organic solvent such as dioxane, N-methylpyrrolidone, dimethylacetamide and the like in the presence of a basic condensing agent such as triethanolamine, alkali carbonate or alkali hydrogen carbonate. At this time, high resolution is obtained by using an esterified product of naphthoquinonediazidesulfonic acid having a mole number of 50% or more, preferably 60% or more based on the total number of moles of the hydroxyl group of the hydroxy compound of the general formula (I). It is preferable because it can be obtained.

In the present invention, the blending ratio of the component (B) is based on the total amount of the alkali-soluble resin as the component (A) and the following (E) a sensitivity improver optionally added.
It is good to select in the range of 10 to 60% by weight, preferably 20 to 50% by weight. According to this mixing ratio, the remaining film ratio, the development contrast, the resolution, the exposure margin, the depth of focus width characteristic,
The effects of the present invention, such as the cross-sectional shape, are further improved.
The component (B) may be used alone or in combination of two or more. The component (B) contains, as an essential component, a quinonediazidesulfonic acid esterified compound of the compound represented by the general formula (I), and the essential component accounts for 20 to 100% by weight, preferably 50% by weight, of the component (B). It may be contained in a proportion of up to 95% by weight.

(C) Sulfonic Acid Halide In the present invention, the component (A) and the component (B)
It is necessary to mix the component (C), that is, at least one sulfonic acid halide represented by the following general formula (II).

[0046]

Embedded image R ¹⁰ —SO ₂ —X (II)

(Wherein, R ¹⁰ represents an alkyl group, an alkyl group having a substituent, an alkenyl group, an aryl group or an aryl group having a substituent, and X represents F or Cl)

Examples of the sulfonic acid halide represented by the general formula (II) include methanesulfonic acid chloride, methanesulfonic acid fluoride, ethanesulfonic acid chloride, n-propanesulfonic acid chloride, and n-propanesulfonic acid chloride.
Alkanesulfonic acid halides having 1 to 12 carbon atoms such as butanesulfonic acid chloride, pentanesulfonic acid chloride, dodecanesulfonic acid chloride; chloromethylsulfonic acid chloride, dichloromethylsulfonic acid chloride, trichloromethylsulfonic acid chloride,
-1 carbon atom such as chloroethylsulfonic acid chloride
To 12 substituted alkanesulfonic acid halides; alkenesulfonic acid halides having 2 to 3 carbon atoms such as ethylenesulfonic acid chloride and 1-propene-1-sulfonic acid chloride; benzenesulfonic acid chloride, benzenesulfonic acid fluoride, benzyl Arylsulfonic acid halides such as sulfonic acid chloride and 1-naphthalenesulfonic acid chloride; p-toluenesulfonic acid chloride, p-ethylbenzenesulfonic acid chloride, p-
Alkyl-, alkenyl-, such as styrenesulfonic acid chloride and p-methoxybenzenesulfonic acid chloride;
And alkoxy-substituted arylsulfonic acid halides. Among these, alkane sulfonic acid halides, aryl sulfonic acid halides and alkyl-substituted aryl sulfonic acid halides are preferable because of their excellent balance of cross-sectional shape, exposure latitude and depth of focus. Among them, benzyl sulfonic acid chloride and naphthalene sulfone are preferable. Acid chloride and p-toluenesulfonic acid chloride are particularly preferred.

The resist solution to which the above-mentioned sulfonic acid halide is added does not need to be acidic, and it is preferable that the resist solution be closer to neutral from the viewpoint of storage stability and stability over time.
Further, in the step of drying the resist film, it is preferable that the compound does not have a very low boiling point so as not to be sublimated, and p-toluenesulfonic acid chloride having a monocyclic aryl group is preferable as those having excellent overall properties. No. These sulfonic acid halides may be used alone or in combination of two or more.

By adding the above component (C),
The residual film ratio is improved, and the effect of making the tapered resist pattern closer to a rectangular shape is obtained.However, the amount of addition depends on the type of the underlying substrate and the underlying layer, the type of the photosensitive agent, and the like. When is used, a large amount can be added out of the following addition amount range, and the most optimal range can be selected according to the occasion. However, the usual addition amount is 0.0
It is added in the range of 1 to 5% by weight, preferably 0.1 to 1% by weight. According to this range, the effect of preventing film loss against defocus on the plus side is further improved, and the occurrence rate of pattern collapse of an isolated pattern with respect to defocus on the minus side can be further reduced.

In the present invention, the component (D), that is, the following general formula (III):

[0052]

Embedded image

(Wherein R ¹¹ and R ¹² may be the same or different and each represents a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group, alkenyl group or alkoxy group having 1 to 6 carbon atoms) Represents)

A polyhydroxy compound represented by the following formula can be blended. By adding the component (D), the exposure latitude and the residual film ratio are improved.

In the definition of R ¹¹ and R ¹² in the general formula (III), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group and an isobutyl group. , Sec-butyl group, t-butyl group, pentyl group, hexyl group and the like. Further, specific examples of the alkenyl group having 1 to 6 carbon atoms include a vinyl group and an allyl group. As the alkoxy group having 1 to 6 carbon atoms, specifically, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentyloxy group And a hexyloxy group.

As the polyhydroxy compound represented by the general formula (III), specifically, the following compounds are preferably exemplified, and these may be used in combination of two or more as necessary. .

[0057]

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[0058]

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[0059]

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[0060]

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Among them, 1,4-bis [1
-(3-Cyclohexyl-4-hydroxy-6-methylphenyl) isopropyl] benzene is preferred.

The compounding ratio of the component (D) can be appropriately changed according to the type of the base substrate and the base layer, the type of the photosensitive agent, and the like. Preferably, it is added in the range of 1 to 5% by weight. Within this range, the effects of the present invention are more favorably exhibited.

(E) Sensitivity Enhancer In the composition of the present invention, a sensitivity enhancer (sensitizer) can be contained, if desired, as long as the preferable performance is not impaired. As such, at least one selected from the hydroxyaryls represented by the general formula (IV) can be contained.

The hydroxyaryls represented by the general formula (IV) as a sensitivity improver include bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxy in the compounds exemplified above. Phenylmethane, 2,4
-Bis (3,5-dimethyl-4-hydroxyphenylmethyl) -6-methylphenol, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5 -Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-
Hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4
-Hydroxyphenyl) ethyl] benzene, 1- [1-
(3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2,6-bis [1-
(2,4-dihydroxyphenyl) isopropyl] -4
-Methylphenol, 4,6-bis [1- (4-hydroxyphenyl) isopropyl] resorcin, 4,6-bis (3,5-dimethoxy-4-hydroxyphenylmethyl) pyrogallol, 4,6-bis (3 5-dimethyl-
4-hydroxyphenylmethyl) pyrogallol, 2,6
-Bis (3-methyl-4,6-dihydroxyphenylmethyl) -4-methylphenol, 2,6-bis (2
3,4-trihydroxyphenylmethyl) -4-methylphenol, 1,1-bis (4-hydroxyphenyl)
Cyclohexane and the like are preferred. Among them, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4
-Hydroxy-3,5-dimethylphenyl) -3,4-
Dihydroxyphenylmethane, 2,4-bis (3,5-
Dimethyl-4-hydroxyphenylmethyl) -6-methylphenol and 4,6-bis [1- (4-hydroxyphenyl) isopropyl] resorcin are particularly preferred.

(E) The compounding ratio of the sensitivity improver is selected in the range of 5 to 50% by weight, preferably 10 to 35% by weight, based on the alkali-soluble resin as the component (A). In the present invention, it is more preferable to use the (E) sensitivity improver in the above range, since the exposure latitude, the resolution, and the depth of focus characteristics are further improved, and the sensitivity is also excellent.

The composition of the present invention may further contain, if necessary, a compatible additive, an ultraviolet absorber for preventing halation such as 2,2 ', 4,4'-tetrahydroxybenzophenone, -Dimethylamino-2 ', 4'
-Dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4- Diethylaminoazobenzene, curcumin and the like, and a surfactant for preventing striation, for example, Florade FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), F-Top EF122A,
Fluorinated surfactants such as EF122B, EF122C, and EF126 (trade name, manufactured by Tochem Products Co., Ltd.) can be added and contained as long as the object of the present invention is not hindered.

The composition of the present invention is preferably used in the form of a solution by dissolving the components (A), (B) and (C) and various components added as necessary in a suitable solvent. . Examples of such a solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or Polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether and monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and ethyl lactate, methyl acetate, ethyl acetate and butyl acetate And esters such as methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate. That. These may be used alone or as a mixture of two or more.

One example of a preferred method of using the composition of the present invention is as follows. First, the components (A), (B) and (C), and various components added as required, are described above. Dissolve in a suitable solvent like this, apply it on a silicone wafer or a support on which an antireflection film is formed with a spinner or the like, dry it to form a photosensitive layer, and then emit a UV light source, for example, a low pressure light source. Mercury lamp,
Exposure through a desired mask pattern using a high-pressure mercury lamp, ultra-high-pressure mercury lamp, arc, xenon lamp, or the like,
Alternatively, irradiation is performed while scanning an electron beam. Next, when this is immersed in a developing solution, for example, an alkaline aqueous solution such as a 1 to 10% by weight aqueous solution of tetramethylammonium hydroxide (TMAH), the exposed portions are dissolved and removed, and an image faithful to the mask pattern can be obtained. According to the composition of the present invention, it is possible to form a resist pattern having a good shape even when the position of the focal point is shifted to the plus side or the minus side. To provide an anti-reflection coating on the
Method) can be usefully applied to a multilayer resist material employing the above method.

[0069]

The present invention will be further described below with reference to examples and comparative examples. The physical properties of the positive photoresist composition were determined as follows. (1) Exposure margin: A sample is applied on a silicon wafer having an anti-reflection layer formed thereon using a spinner, and dried on a hot plate at 90 ° C. for 90 seconds to form a film having a thickness of 0.85.
A μm resist film was obtained. A reduction projection exposure apparatus N
SR-2005i10D (manufactured by Nikon Corporation, NA = 0.5
After exposure at 0.1 to 0.01 second intervals using 7), PEB (post-exposure bake) treatment is performed at 110 ° C. for 90 seconds, and a 2.38 wt% aqueous solution of tetramethylammonium hydroxide is used. When developed at 60 ° C. for 60 seconds, washed with water for 30 seconds, and dried, the exposure time at which the film thickness of the exposed portion after development becomes 0 is Eth, and the exposure time at which the line and space width is formed 1: 1 is Milliseconds as Eop (m
s), and the exposure latitude was expressed as Eop / Eth.

(2) Cross-sectional shape: (2-1) Positive focus side: film thickness 0.85 μm, width 0.3
The cross-sectional shape of the isolated resist pattern of 5 μm was observed by a SEM (scanning electron microscope) photograph, and 0.6
When the cross-sectional shape of the pattern when the μm focal point deviated, the one with a film reduction rate of less than 10% was A, the one with 10% to 50% was B, and the one with more than 50% was C.

(2-2) Focus minus side: film thickness 0.85
The cross-sectional shape of the isolated resist pattern having a width of 0.35 μm and a width of 0.35 μm was observed by an SEM (scanning electron microscope) photograph. A was not observed, B was an inverted tapered shape or a pattern was thinned, and C was a pattern collapsed.

(3) Depth of focus characteristic: reduction projection exposure apparatus NSR-2005i10D (Nikon Corporation, NA = 0.5)
Using 7), Eop (exposure amount required to form a 0.35 μm line and space width of 1: 1) is set as a reference exposure amount. An SEM photograph of the isolated resist pattern obtained by development was observed. From the SEM photograph, the maximum value (μm) of defocus at which a rectangular resist pattern of 0.35 μm was obtained was defined as the depth of focus width characteristic.

The anti-reflection layer was formed as follows. Mx-750 (manufactured by Sanwa Chemical Co., Ltd.), a melamine having an average of 3.7 methoxymethyl groups on a silicon wafer, 2,2 ′, 4,4′-tetrahydroxybenzophenone and glycidyl methacrylate and methyl methacrylate A solution in which the copolymer was dissolved in propylene glycol monomethyl ether acetate was applied, dried, and baked at 180 ° C. to form an antireflection layer.

Example 1 An alkali obtained by condensing m-cresol, p-cresol, and 2,3,5-trimethylphenol in a molar ratio of 4: 3: 3 with formalin in a conventional manner. The low molecular weight fraction of the soluble resin was removed to obtain an alkali soluble resin having a weight average molecular weight of 3,800. Similarly, a mixture of m-cresol and p-cresol in a molar ratio of 1: 1 was used to obtain a weight average molecular weight of 40.
00 alkali-soluble resin was obtained. Then, a resin component 1 in which both alkali-soluble resins were mixed at a weight ratio of 1: 1.
To 100 parts by weight, 27 parts by weight of bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane as a sensitivity improver, and 2,4-bis [4-hydroxy-3 (4) as a photosensitizer. -Hydroxybenzyl) -5
-Methylbenzyl] -6-cyclohexylphenol (a1) and 1 mole of naphthoquinone-1,2-diazide-5
-Esterified product with 3 mol of sulfonyl chloride (A
1) 43 parts by weight, further 0.5 parts by weight of p-toluenesulfonic acid chloride and 480 parts by weight of 2-heptanone were added and dissolved, followed by filtration using a membrane filter having a pore size of 0.2 μm to obtain a positive type A photoresist composition was prepared.

(Example 2) In Example 1, A1 was converted to an esterified product of 2,4-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol (A2). A positive photoresist composition was prepared in the same manner as in Example 1 except for changing the composition.

Example 3 In Example 1, A1 was converted to an esterified product of 2,6-bis [4-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -4-cyclohexylphenol (A3). A positive photoresist composition was prepared in the same manner as in Example 1 except for changing the composition.

(Examples 4 to 6) In Examples 1 to 3, 1,4-bis [1- (3-cyclohexyl-4-hydroxy-6-methylphenyl) isopropyl] benzene (BCIB) was used. A positive photoresist composition was prepared in the same manner as in Examples 1 to 3, except that 3.5 parts by weight was separately added. Examples 4 to 6 respectively.

Comparative Example 1 The procedure of Example 1 was repeated, except that A1 was replaced with an esterified product of bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane (B1). A positive photoresist composition was prepared in the same manner as in Example 1.

Comparative Example 2 A positive photoresist composition was prepared in the same manner as in Example 1 except that p-toluenesulfonic acid chloride was not added.

Table 1 shows the physical properties (1), (2) and (3) of the compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2.

[0081]

[Table 1]

[0082]

According to the present invention, particularly in the formation of an isolated pattern, not a dense pattern of lines and spaces (L & S), the residual film ratio is good, and the development contrast between exposed and unexposed areas is excellent. Provided are a positive photoresist composition capable of forming a resist pattern having excellent resolution, exposure latitude, depth of focus characteristics, and cross-sectional shape, and a multilayer resist material.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/30 502R 573 574 (72) Inventor Toshiaki Nakayama 150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Pref. Inside the corporation

Claims (7)

[Claims] (A) an alkali-soluble resin; (B) the following general formula (I): (Wherein, R ^{1 to} R ⁹ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, or alkoxy group having 1 to 5 carbon atoms) (C) at least one kind of a quinonediazide group-containing compound in which a part or all of the hydroxyl groups is quinonediazidesulfonic acid ester, and (C) the following general formula (II): R ¹⁰ —SO ₂ —X (II) Wherein R ¹⁰ represents an alkyl group, an alkyl group having a substituent, an alkenyl group, an aryl group or an aryl group having a substituent, and X represents F or Cl. A positive photoresist composition comprising: 2. The method according to claim 1, further comprising (D) the following general formula (III): (Wherein R ¹¹ and R ¹² may be the same or different and each represent a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an alkenyl group, or an alkoxy group. The positive photoresist composition according to claim 1, comprising a compound represented by the formula: Further, (E) as a sensitivity improver, the following general formula (IV): (Wherein, R ^{13 to} R ²⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms,
R ^{21 to} R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms. groups, bonded to R ^21, carbon atoms chains 3
To 6 or a ring represented by the following chemical formula: (Wherein, R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, or a cycloalkyl group; A, b represents 1 to 3
D represents an integer of 0 to 3; n represents 0 to 2
The positive photoresist composition according to claim 1 or 2, comprising a hydroxyaryl represented by the following formula: 4. The composition according to claim 1, wherein the content of the component (C) is 0.01 to 5% by weight based on the total solid content of the composition. Positive photoresist composition. 5. The positive photoresist composition according to claim 2, wherein the content of the component (D) is 0.01 to 10% by weight based on the total solid content of the composition. 6. The compounding ratio of (B) the quinonediazide group-containing compound is 10 to 6 with respect to the total amount of (A) the alkali-soluble resin and (E) a sensitivity improver added as needed.
The positive photoresist composition according to any one of claims 1 to 5, which is 0% by weight. 7. A multilayer resist material comprising an anti-reflection layer on a substrate and a positive photoresist layer on the anti-reflection layer, wherein the positive photoresist layer is formed of a material.
A multilayer resist material formed from the positive photoresist composition according to any one of the above.